Production of Polyolefins with Internal Unsaturation Structures Using a Metallocene Catalyst System

ABSTRACT

This invention relates to a process to polymerize olefins, particularly to produce ethylene polymers with internal unsaturation structures.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention relates to a process to polymerize olefins, particularlyto produce ethylene polymers with internal unsaturation structures.

FIELD OF THE INVENTION

This invention relates to a process to polymerize olefins, particularlyto produce ethylene polymers with internal unsaturation structures.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hence,there is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

Catalysts for olefin polymerization are often based on hafnocenes ascatalyst precursors, which are activated either with the help of analumoxane, or with an activator containing a non-coordinating anion. Forexample, U.S. Pat. No. 7,157,531 discloses bis(n-propyl Cp)Hf Me₂catalyst compounds used to make ethylene polymer having a controlledcomonomer distribution.

Other references of interest include: U.S. Pat. No. 6,242,545; U.S. Pat.No. 6,956,088; US 2008/0038533; U.S. Pat. No. 6,936,675; Macromolecules2005, 38, 6988; and Macromolecules 2014, 47, 3782.

However, it is a need in the art to develop a new process for thepolymerization of olefins and improved catalyst systems suitable for theprocess, in order to achieve specific and balanced polymer properties,including high molecular weight, increased comonomer incorporation, lowcontent of long chain branching and high internal unsaturationstructures within the backbone of polymers.

SUMMARY OF THE INVENTION

This invention relates to a process to polymerize olefins comprising:

1) contacting olefin monomers with a catalyst system comprising anactivator and a bis-cyclopentadienyl metallocene compound represented bythe formula:

wherein:

M is Hf;

each X¹ and X² is independently, a hydrocarbyl radical having from 1 to20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide,diene, amine, phosphine, ether, or X¹ and X² may form a part of a fusedring or a ring system;each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen,halide, alkoxide or a C₁ to C₄₀ (preferably C₁ to C₂₀) substituted orunsubstituted hydrocarbyl group, provided that at least one of R¹, R²,R³, R⁴, R⁶, R⁷, R⁸, and R⁹, is a linear C₃ to C₂₀ substituted orunsubstituted hydrocarbyl group;T is a group 14 atom (preferably, silicon or germanium; more preferably,silicon); each R^(a) and R^(b) is independently, a C₁ to C₄₀ substitutedor unsubstituted hydrocarbyl, (preferably a C₁ to C₂₀ substituted orunsubstituted alkyl, or a C₆ to C₂₀ substituted or unsubstituted aryl(such as phenyl, and substituted phenyl groups);wherein the bis-cyclopentadienyl metallocene compound generates hydrogenand the polymerization occurs in the presence of hydrogen, preferably atleast 200 ppm hydrogen; and2) obtaining a polymer having:

a) an internal unsaturation of 50% or more;

b) a melt index of 20 dg/min or less; and

c) a g′vis of 0.95 or more.

This invention further relates to a catalyst system comprising anactivator and the bis-cyclopentadienyl metallocene compound representedby the above formula herein.

This invention further relates to a polymer produced by the processdescribed herein, wherein the polymer has: a) an internal unsaturationof 50% or more; b) a melt index of 20 dg/min or less; and c) a g′vis of0.95 or more.

This invention further relates to an ethylene polymer produced by theprocess described herein, wherein the polymer has: a) an internalunsaturation of 60% or more, b) a melt index of 1.0 dg/min or less; andc) a g′vis of 0.95 or more.

The inventors interestingly found that the produced polymer has acombination of high Mw capability, improved hexene response, low contentof long chain branching, and particularly high levels of internalunsaturation structures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the ¹H NMR spectra of the olefinic region of the polymer madeusing supported Catalyst B in Table 1.

FIG. 2 is the ¹H NMR spectra of the olefinic region of the polymer madeusing supported Catalyst A in Table 1.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inCHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27, (1985). Therefore, a“group 4 metal” is an element from group 4 of the Periodic Table, e.g.,Hf, Ti, or Zr.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mol %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mol % propylene derivedunits, and so on.

For the purposes of this invention, ethylene shall be considered anα-olefin.

For purposes of this invention and claims thereto, the term“substituted” means that a hydrogen group has been replaced with aheteroatom, or a heteroatom-containing group.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity (PDI), is defined to be Mwdivided by Mn. Unless otherwise noted, all molecular weight units (e.g.,Mw, Mn, Mz) are g/mol. The following abbreviations may be used herein:Me is methyl, Et is ethyl, Pr is propyl, cPR is cyclopropyl, nPr isn-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu isisobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph isphenyl, Bn is benzyl, and MAO is methylalumoxane.

A “catalyst system” is a combination of at least one catalyst compound,at least one activator, an optional co-activator, and an optionalsupport material. For the purposes of this invention and the claimsthereto, when catalyst systems are described as comprising neutralstable forms of the components, it is well understood by one of ordinaryskill in the art that the ionic form of the component is the form thatreacts with the monomers to produce polymers.

In the description herein, the metallocene compound may be described asa catalyst precursor, a pre-catalyst compound, catalyst compound or atransition metal compound, and these terms are used interchangeably. Ametallocene catalyst is defined as an organometallic compound with twoπ-bound cyclopentadienyl moieties or substituted cyclopentadienylmoieties.

For purposes of this invention and claims thereto in relation tometallocene compounds, the term “substituted” means that a hydrogengroup has been replaced with a hydrocarbyl group, a heteroatom, or aheteroatom-containing group. For example, methyl cyclopentadiene (Cp) isa Cp group substituted with a methyl group.

Room temperature (RT) is 23° C. unless otherwise indicated.

For purposes of this disclosure, “hydrocarbyl radical” is defined to beC₁-C₁₀₀ radicals, that may be linear, branched, or cyclic, and whencyclic, aromatic or non-aromatic. Examples of such radicals include, butare not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and thelike including their substituted analogues. Substituted hydrocarbylradicals are radicals in which at least one hydrogen atom of thehydrocarbyl radical has been substituted with at least one heteroatom orhetroatom-containing group (i.e., halogen (such as Br, Cl, F or I) or afunctional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like), or where at least oneheteroatom has been inserted within a hydrocarbyl ring.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or thee ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S. As usedherein, the term “aromatic” also refers to pseudoaromatic heterocycles,which are heterocyclic substituents that have similar properties andstructures (nearly planar) to aromatic heterocyclic ligands, but are notby definition aromatic; likewise the term aromatic also refers tosubstituted aromatics.

Reference to a hydrocarbyl, alkyl or aryl group without specifying aparticular isomer (e.g., butyl) expressly discloses all isomers (e.g.,n-butyl, iso-butyl, sec-butyl, and tert-butyl).

“Complex” as used herein, is also often referred to as catalystprecursor, pre-catalyst, catalyst, catalyst compound, transition metalcompound, or transition metal complex. These words are usedinterchangeably. Activator and cocatalyst are also used interchangeably.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments, a co-activatorcan be pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

Process

This invention relates to a process to polymerize olefins comprising:

1) contacting olefin monomers (such as ethylene and, optionally, a C₃ toC₁₂ comonomer (e.g., propylene, butene, hexene, and/or octene)) with acatalyst system comprising an activator (such as an alumoxane or anon-coordinating anion) and a bis-cyclopentadienyl metallocene compoundrepresented by the formula:

wherein:

M is Hf;

each X¹ and X² is independently, a hydrocarbyl radical having from 1 to20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide,diene, amine, phosphine, ether, or X¹ and X² may form a part of a fusedring or a ring system;each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen,halide, alkoxide or a C₁ to C₄₀ substituted or unsubstituted hydrocarbylgroup, (preferably, each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is,independently, a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup), provided that at least one of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹is a linear C₃ to C₂₀ substituted or unsubstituted hydrocarbyl group,(preferably at least one of R⁶, R⁷, R⁸, and R⁹ and at least one of R¹,R², R³, R⁴, is a linear C₃ to C₂₀ substituted or unsubstitutedhydrocarbyl group, preferably at least one of R², R³, R⁷ and R⁸ is a C₃to C₁₀ linear alkyl group);T is a group 14 atom (preferably, silicon or germanium; more preferably,silicon);each R^(a) and R^(b) is independently, a hydrocarbyl or a substitutedhydrocarbyl, (preferably a substituted or unsubstituted C₁ to C₄₀ alkyl,or a C₆ to C₂₀ substituted or unsubstituted aryl preferably, each R^(a)and R^(b) is, independently selected from the group consisting ofsubstituted or unsubstituted C₁ to C₂₀ alkyl, phenyl, and substitutedphenyl groups);wherein the bis-cyclopentadienyl metallocene compound generates hydrogenand the polymerization occurs in the presence of hydrogen, preferably atleast 200 ppm hydrogen; and2) obtaining a polymer having:

a) internal unsaturations of 50% or more;

b) a melt index of 20 dg/min or less, preferably 1.0 or less; and

c) a g′vis of 0.95 or more.

Advantageously, the metallocene catalyst (as activated in the catalystsystem) produces hydrogen during the polymerization reaction. Hydrogenproduction is determined by measuring the amount of hydrogen present ina polymerization reaction where no hydrogen has been added to thereaction. The polymerization occurs in the presence of hydrogen,preferably at least 200 ppm hydrogen is present in the polymerizationreaction, preferably at least 400 ppm, preferably at least 600 ppm.Alternately, hydrogen is present in the polymerization reactor at apartial pressure of 0.007 to 345 kPa, preferably from 0.07 to 172 kPa,preferably 0.7 to 70 kPa. Some or all of the hydrogen may be generatedby the catalyst system. Even though the metallocene catalyst produceshydrogen, extra hydrogen may be added to the polymerization reaction.

Bis-Cyclopentadienyl Metallocene Compounds

As used herein, the bis-cyclopentadienyl metallocene compounds usefulherein are represented by the formula:

wherein:

M is Hf;

each X¹ and X² is independently, a hydrocarbyl radical having from 1 to20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide,diene, amine, phosphine, ether, or X¹ and X² may form a part of a fusedring or a ring system;each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen,halide, alkoxide or a C₁ to C₄₀ substituted or unsubstituted hydrocarbylgroup, (preferably, each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is,independently, a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup) provided that at least one (preferably at least two) of R¹, R²,R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is a linear C₃ to C₂₀ substituted orunsubstituted hydrocarbyl group; preferably at least one of R² and R³and at least one of R⁷ and R⁸ is a C₃ to C₁₀ linear alkyl group,preferably a n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, or n-decyl group;T is a group 14 atom (preferably, silicon or germanium; more preferably,silicon); andeach R^(a) and R^(b) is independently, a hydrocarbyl or a substitutedhydrocarbyl, (preferably a substituted or unsubstituted C₁ to C₂₀ alkyl,a C₆ to C₂₀ substituted or unsubstituted aryl preferably, each R^(a) andR^(b) is, independently selected from the group consisting ofsubstituted or unsubstituted C₁ to C₁₂ alkyl groups and phenyl andsubstituted phenyl groups).

In any embodiment described herein, each X¹ and X² is independently,selected from the group consisting of: Cl, Br, I, methyl, ethyl, propyl,butyl, pentyl, heptyl, octyl, nonyl, decyl, undecy, dodecyl, and isomersthereof;

In any embodiment described herein, R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹is, independently, hydrogen, methyl, ethyl, propyl, butyl, pentyl,heptyl, octyl, nonyl, decyl, undecy, dodecyl, or an isomer thereof,provided that at least one of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹(preferably at least one of R², R³, R⁷ and R⁸, preferably at least oneof R² and R³ and at least one of R⁷ and R⁸) is, independently, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl.

In any embodiment described herein, at least one of R² and R³ and atleast one of R⁷ and R⁸, is a C₃ to C₁₀ linear alkyl group, preferably an-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, orn-decyl group.

In any embodiment described herein, at least one of R⁶, R⁷, R⁸, and R⁹and at least one of R¹, R², R³, R⁴, is a linear C₃ to C₂₀ substituted orunsubstituted hydrocarbyl group, preferably a C₃ to C₁₀ linear alkylgroup, preferably a n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,n-octyl, n-nonyl, or n-decyl group.

In any embodiment described herein, T is silicon.

Examples of C₆ to C₂₀ substituted or unsubstituted aryl groups includephenyl, benzyl, tolyl, carbazolyl, naphthyl, and the like.

In any embodiment described herein, each R^(a) and R^(b) isindependently, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl,nonyl, decyl, undecy, dodecyl, phenyl, methyl phenyl, ethylphenyl,propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl,octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl,phenylphenyl, or an isomer thereof.

In any embodiment described herein, each R^(a) and R^(b) isindependently, a phenyl group substituted with 1, 2, 3, 4, or 5 groups,preferably groups independently selected from the group consisting of:phenyl, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, nonyl,decyl, undecy, dodecyl, methyl phenyl, ethylphenyl, propylphenyl,butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl,nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl,and isomers thereof.

In any embodiment described herein, each R^(a) and/or R^(b) may beindependently selected from the group consisting of phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl,hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl,undecylphenyl, dodecylphenyl, phenylphenyl, fluorophenyl, chlorophenyl,bromophenyl, methoxyphenyl, trifluoromethylphenyl, dimethylaminophenyl,trimethylsilylphenyl, triethylsilylphenyl, tripropylsilylphenyl,(trimethylsilyl)ethylphenyl, 3,5-di(isopropyl)phenyl,3,5-di(isobutyl)phenyl, 3,5-di(tert-butyl)phenyl, carbazol-9-yl,di-tert-butylcarbazol-9-yl, 2,3,4,5,6,7,8,9-octahydrocarbazol-1anthracen-9-yl, 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl, naphthyl,fluoren-9-yl, 9-methylfluoren-9-yl,1,2,3,4,5,6,7,8-octahydrofluoren-9-yl, or9-methyl-1,2,3,4,5,6,7,8-octahydrofluoren-9-yl, and isomers thereof.

In any embodiment described herein, at least one of R⁶, R⁷, R⁸, and R⁹and at least one of R¹, R², R³, R⁴, is a linear C₃ to C₂₀ substituted orunsubstituted hydrocarbyl group, preferably a C₃ to C₁₀ linear alkylgroup, preferably a n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,n-octyl, n-nonyl, or n-decyl group and each R^(a) and R^(b) isindependently, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, phenyl, methyl phenyl, ethylphenyl,propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl,octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl,phenylphenyl, or an isomer thereof.

In some preferred embodiments, each X¹ and X² is, independently,selected from the group consisting of halides and C₁ to C₅ alkyl groups;each X¹ and X² is, independently, selected from the group consisting ofchlorides, fluorides, methyl, ethyl, propyl and butyl groups; at leastone of R⁶, R⁷, R⁸, and R⁹ and at least one of R¹, R², R³, R⁴, is alinear C₃ to C₂₀ substituted or unsubstituted hydrocarbyl group; eachR², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, a linear C₃ to C₂₀alkyl group; each R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently,selected from the group consisting of n-propyl, n-butyl, n-pentyl, andn-hexyl groups; each R^(a) and R^(b) is, independently selected from thegroup consisting of phenyl and substituted phenyl groups.

The metallocene compounds that are particularly useful in this inventioninclude one or more of:

-   diphenylsilylbis(n-propylcyclopentadienyl)hafniumX¹X²,-   diphenylsilylbis(n-butylcyclopentadienyl)hafniumX¹X²,-   diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X²,-   diphenylsilyl (n-propyl cyclopentadienyl)(n-butyl    cyclopentadienyl)hafniumX¹X²,-   diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X²,-   dimethylsilylbis(n-propylcyclopentadienyl)hafniumX¹X²,-   dimethylsilylbis(n-butylcyclopentadienyl)hafniumX¹X²,-   dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X²,-   dimethylsilyl (n-propyl cyclopentadienyl)(n-butyl    cyclopentadienyl)hafniumX¹X², and-   dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X²,    wherein each X¹ and X² is, independently, selected from the group    consisting of chlorides, fluorides, methyl, ethyl, propyl, butyl    groups and isomers thereof.

In a preferred embodiment in any of the processes described herein, onemetallocene compound is used, e.g., the metallocene compounds are notdifferent. For purposes of this invention, one metallocene compound isconsidered different from another if they differ by at least one atom.For example, “bisindenyl zirconium dichloride” is different from(indenyl)(2-methylindenyl) zirconium dichloride” which is different from“(indenyl)(2-methylindenyl) hafnium dichloride.” Metallocene compoundsthat differ only by isomer are considered the same for purposes of thisinvention, e.g., rac-dimethylsilylbis(2-methyl 4-phenylindenyl)hafniumdimethyl is considered to be the same as meso-dimethylsilylbis(2-methyl4-phenylindenyl)hafnium dimethyl.

In some embodiments, two or more different metallocene compounds arepresent in the catalyst system used herein. In some embodiments, two ormore different metallocene compounds are present in the reaction zonewhere the process(es) described herein occur. When two transition metalcompound based catalysts are used in one reactor as a mixed catalystsystem, the two transition metal compounds are preferably chosen suchthat the two are compatible. A simple screening method such as by ¹H or¹³C NMR, known to those of ordinary skill in the art, can be used todetermine which transition metal compounds are compatible. It ispreferable to use the same activator for the transition metal compounds,however, two different activators, such as a non-coordinating anionactivator and an alumoxane, can be used in combination. If one or moretransition metal compounds contain an X¹ or X² ligand which is not ahydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxaneshould be contacted with the transition metal compounds prior toaddition of the non-coordinating anion activator.

The two transition metal compounds (pre-catalysts) may be used in anyratio. Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, andalternatively 5:1 to 50:1. The particular ratio chosen will depend onthe exact pre-catalysts chosen, the method of activation, and the endproduct desired. In a particular embodiment, when using the twopre-catalysts, where both are activated with the same activator, usefulmole percents, based upon the molecular weight of the pre-catalysts, are10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50%B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99%A to 1 to 10% B.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of themetallocene compounds described above by converting the neutralmetallocene compound to a catalytically active metallocene compoundcation.

After the compounds described above have been synthesized, catalystsystems may be formed by combining them with activators in any mannerknown from the literature including by supporting them for use in slurryor gas phase polymerization. The catalyst systems may also be added toor generated in solution polymerization or bulk polymerization (in themonomer). The catalyst system typically comprises a compound asdescribed above and an activator such as alumoxane or a non-coordinatinganion.

Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnon-coordinating or weakly coordinating anion.

Alumoxane Activators

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst system. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O-sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxide,or amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator typically at up to a5000-fold molar excess Al/M over the metallocene compound (per metalcatalytic site). The minimum activator-to-catalyst-compound is a 1:1molar ratio. Alternate preferred ranges include from 1:1 to 500:1,alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, oralternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to metallocene compound transition metal less than500:1, preferably less than 300:1, preferably less than 100:1,preferably less than 1:1.

Non-Coordinating Anion Activators

A non-coordinating anion (NCA) is defined to mean an anion that eitherdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA coordinatesweakly enough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer, can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the non-coordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon. A stoichiometric activator canbe either neutral or ionic. The terms ionic activator and stoichiometricionic activator can be used interchangeably. Likewise, the terms neutralstoichiometric activator and Lewis acid activator can be usedinterchangeably. The term non-coordinating anion includes neutralstoichiometric activators, ionic stoichiometric activators, ionicactivators, and Lewis acid activators.

“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral transition metal compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with this invention are those that are compatible, stabilizethe transition metal cation in the sense of balancing its ionic chargeat +1, and yet retain sufficient lability to permit displacement duringpolymerization.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

The catalyst systems of this invention can include at least onenon-coordinating anion (NCA) activator.

In a preferred embodiment, boron containing NCA activators representedby the formula below can be used:

Z_(d) ⁺(A^(d−))

wherein:Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H ishydrogen;(L-H) is a Bronsted acid; A^(d−) is a boron containing non-coordinatinganion having the charged−; andd is 1, 2, or 3.

The cation component, Z_(d) ⁺ may include Bronsted acids such as protonsor protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thebulky ligand metallocene containing transition metal catalyst precursor,resulting in a cationic transition metal species.

The activating cation Z_(d) ⁺ may also be a moiety such as silver,tropylium, carboniums, ferroceniums and mixtures, preferably carboniumsand ferroceniums. Most preferably Z_(d) ⁺ is triphenyl carbonium.Preferred reducible Lewis acids can be any triaryl carbonium (where thearyl can be substituted or unsubstituted, such as those represented bythe formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl), preferably the reducible Lewis acids in formula (14) aboveas “Z” include those represented by the formula: (Ph₃C), where Ph is asubstituted or unsubstituted phenyl, preferably substituted with C₁ toC₄₀ hydrocarbyls or substituted C₁ to C₄₀ hydrocarbyls, preferably C₁ toC₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics,preferably Z is a triphenylcarbonium.

When Z_(d) ⁺ is the activating cation (L-H)_(d)+, it is preferably aBronsted acid, capable of donating a proton to the transition metalcatalytic precursor resulting in a transition metal cation, includingammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof,preferably ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxomiuns from ethers such as dimethyl ether, diethyl ether,tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers, tetrahydrothiophene, and mixtures thereof.

The anion component A^(d−) includes those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6(preferably 1, 2, 3, or 4); n−k=d; M is an element selected from Group13 of the Periodic Table of the Elements, preferably boron or aluminum,and Q is independently a hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbylradicals, said Q having up to 20 carbon atoms with the proviso that innot more than 1 occurrence is Q a halide. Preferably, each Q is afluorinated hydrocarbyl group having 1 to 20 carbon atoms, morepreferably each Q is a fluorinated aryl group, and most preferably eachQ is a pentafluoryl aryl group. Examples of suitable A^(d−) also includediboron compounds as disclosed in U.S. Pat. No. 5,447,895, which isincorporated herein by reference.

Illustrative, but not limiting examples of boron compounds, which may beused as an activating cocatalyst are the compounds described as (andparticularly those specifically listed as) activators in U.S. Pat. No.8,658,556, which is incorporated herein by reference.

Most preferably, the ionic stoichiometric activator Z_(d) ⁺(A^(d−)) isone or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

Bulky activators are also useful herein as NCAs. “Bulky activator” asused herein refers to anionic activators represented by the formula:

wherein:each R₁ is, independently, a halide, preferably a fluoride;Each Ar is a substituted or unsubstituted aryl group (preferably asubstituted or unsubstituted phenyl), preferably substituted with C₁ toC₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group);wherein R₂ and R₃ can form one or more saturated or unsaturated,substituted or unsubstituted rings (preferably R₂ and R₃ form aperfluorinated phenyl ring); and L is a neutral Lewis base; (L-H)⁺ is aBronsted acid;d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

Preferably (Ar₃C)_(d) ⁺ is (Ph₃C)_(d) ⁺, where Ph is a substituted orunsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbylsor substituted C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls oraromatics or substituted C₁ to C₂₀ alkyls or aromatics.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

For a list of particularly useful Bulky activators please see U.S. Pat.No. 8,658,556, which is incorporated herein by reference.

In another embodiment, one or more of the NCA activators is chosen fromthe activators described in U.S. Pat. No. 6,211,105.

Preferred activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C+][B(C₆F₅)₄ ⁻], [Me₃NH+][B(C₆F₅)₄⁻];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

The typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. Alternatepreferred ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to200:1, alternately from 1:1 to 500:1, or alternately from 1:1 to 1000:1.A particularly useful range is from 0.5:1 to 10:1, preferably 1:1 to5:1.

It is also within the scope of this invention that the metallocenecompounds can be combined with combinations of alumoxanes and NCA's (seefor example, U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,453,410; EP 0 573120 B1; WO 94/07928; and WO 95/14044; which discuss the use of analumoxane in combination with an ionizing activator).

Chain Transfer Agents

Useful chain transfer agents are typically alkylalumoxanes, a compoundrepresented by the formula AlR₃, ZnR₂ (where each R is, independently, aC₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl,hexyl octyl or an isomer thereof) or a combination thereof, such asdiethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Scavengers or Co-Activators

In addition to these activator compounds, scavengers or co-activatorsmay be used. Aluminum alkyl or organoaluminum compounds which may beutilized as scavengers or co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxides,such as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins, such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably, the surface area of the support material is in therange from about 100 to about 400 m²/g, pore volume from about 0.8 toabout 3.0 cc/g and average particle size is from about 5 to about 100μm. The average pore size of the support material useful in theinvention is in the range of from 10 to 1000 Å, preferably 50 to about500 Å, and most preferably 75 to about 350 Å. In some embodiments, thesupport material is a high surface area, amorphous silica (surfacearea=300 m²/gm; pore volume of 1.65 cm³/gm). Preferred silicas includethose available under the tradenames of DAVISON 952 or DAVISON 955 bythe Davison Chemical Division of W.R. Grace and Company. In otherembodiments DAVISON 948 is used.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce supported catalyst systems of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator. Insome embodiments, the slurry of the support material is first contactedwith the activator for a period of time in the range of from about 0.5hours to about 24 hours, from about 2 hours to about 16 hours, or fromabout 4 hours to about 8 hours. The solution of the metallocene compoundis then contacted with the isolated support/activator. In someembodiments, the supported catalyst system is generated in situ. In analternate embodiment, the slurry of the support material is firstcontacted with the metallocene compound for a period of time in therange of from about 0.5 hours to about 24 hours, from about 2 hours toabout 16 hours, or from about 4 hours to about 8 hours. The slurry ofthe supported metallocene compound is then contacted with the activatorsolution.

The mixture of the metallocene, activator, and support is heated toabout 0° C. to about 70° C., preferably to about 23° C. to about 60° C.,preferably at room temperature. Contact times typically range from about0.5 hours to about 24 hours, from about 2 hours to about

16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

This invention relates to a process to polymerize olefins comprising:

1) contacting olefin monomers with a catalyst system comprising anactivator and a bis-cyclopentadienyl metallocene compound represented bythe formula:

wherein:

M is Hf;

each X¹ and X² is independently, a hydrocarbyl radical having from 1 to20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide,diene, amine, phosphine, ether, or X¹ and X² may form a part of a fusedring or a ring system;each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen,halide, alkoxide or a C₁ to C₄₀ substituted or unsubstituted hydrocarbylgroup, (preferably, each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is,independently, a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup) provided that at least one of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹is a linear C₃ to C₂₀ substituted or unsubstituted hydrocarbyl group(preferably at least one of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹(preferably at least one of R², R³, R⁷ and R⁸) is a C₃ to C₁₀ linearalkyl group;T is a group 14 atom (preferably, silicon or germanium; more preferably,silicon);each R^(a) and R^(b) is independently, a C₁ to C₄₀ substituted orunsubstituted hydrocarbyl, (preferably a C₁ to C₂₀ substituted orunsubstituted alkyl, or a C₆ to C₂₀ substituted or unsubstituted arylpreferably, each R^(a) and R^(b) is, independently selected from thegroup consisting of substituted or unsubstituted C₁ to C₁₂ alkyl groups,phenyl, and substituted phenyl groups);wherein the bis-cyclopentadienyl metallocene compound generates hydrogenand the polymerization occurs in the presence of hydrogen, preferably atleast 200 ppm hydrogen; and2) obtaining a polymer having:

-   -   a) an internal unsaturation of 50% or more, preferably 60% or        more, preferably 70% or more;    -   b) a melt index of 20 dg/min or less, preferably 1.0 dg/min or        less; and    -   c) a g′vis of 0.95 or more.

In embodiments herein, the invention relates to polymerization processeswhere monomer (such as ethylene), and optionally comonomer, arecontacted with a catalyst system comprising an activator and at leastone metallocene compound, as described above. The metallocene compoundand activator may be combined in any order, and are combined typicallyprior to contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, preferably C₂ to C₂₀ alpha olefins, preferably C₂ to C₁₂alpha olefins, preferably ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene, and isomersthereof. In a preferred embodiment of the invention, the monomercomprises propylene and optional comonomers comprising one or moreethylene or C₄ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, orpreferably C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups. In anotherpreferred embodiment, the monomer comprises ethylene and optionalcomonomers comprising one or more C₃ to C₄₀ olefins, preferably C₄ toC₂₀ olefins, or preferably C₆ to C₁₂ olefins. The C₃ to C₄₀ olefinmonomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, preferablynorbornene, norbornadiene, and dicyclopentadiene.

In a preferred embodiment, one or more dienes are present in the polymerproduced herein at up to 10 wt %, preferably at 0.00001 to 1.0 wt %,preferably 0.002 to 0.5 wt %, even more preferably 0.003 to 0.2 wt %,based upon the total weight of the composition. In some embodiments 500ppm or less of diene is added to the polymerization, preferably 400 ppmor less, preferably 300 ppm or less. In other embodiments, at least 50ppm of diene is added to the polymerization, or 100 ppm or more, or 150ppm or more.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.,di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Polymerization processes of this invention can be carried out in anymanner known in the art. Any suspension, homogeneous, bulk, solution,slurry, or gas phase polymerization process known in the art can beused. Such processes can be run in a batch, semi-batch, or continuousmode. Homogeneous polymerization processes and slurry processes arepreferred. (A homogeneous polymerization process is defined to be aprocess where at least 90 wt % of the product is soluble in the reactionmedia.) A bulk homogeneous process is particularly preferred. (A bulkprocess is defined to be a process where monomer concentration in allfeeds to the reactor is 70 vol % or more.) Alternately, no solvent ordiluent is present or added in the reaction medium, (except for thesmall amounts used as the carrier for the catalyst system or otheradditives, or amounts typically found with the monomer; e.g., propane inpropylene). In another embodiment, the process is a slurry process. Asused herein the term “slurry polymerization process” means apolymerization process where a supported catalyst is employed andmonomers are polymerized on the supported catalyst particles. At least95 wt % of polymer products derived from the supported catalyst are ingranular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins, which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In a preferred embodiment, aliphatichydrocarbon solvents are used as the solvent, such as isobutane, butane,pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, andmixtures thereof; cyclic and alicyclic hydrocarbons, such ascyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, andmixtures thereof. In another embodiment, the solvent is not aromatic,preferably aromatics are present in the solvent at less than 1 wt %,preferably less than 0.5 wt %, preferably less than 0 wt %, based uponthe weight of the solvents.

In a preferred embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less,preferably 40 vol % or less, or preferably 20 vol % or less, based onthe total volume of the feedstream. Preferably the polymerization is runin a bulk process.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired ethylene polymers. Typical temperaturesand/or pressures include a temperature in the range of from about 0° C.to about 300° C., preferably about 20° C. to about 200° C., preferablyabout 35° C. to about 150° C., preferably from about 40° C. to about120° C., preferably from about 45° C. to about 80° C.; and at a pressurein the range of from about 0.35 MPa to about 10 MPa, preferably fromabout 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about4 MPa.

In a typical polymerization, the run time of the reaction is up to 300minutes, preferably in the range of from about 5 to 250 minutes, orpreferably from about 10 to 120 minutes.

In some embodiments, hydrogen is present in the polymerization reactorat a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferablyfrom 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig(0.7 to 70 kPa).

In an alternate embodiment, the activity of the catalyst is at least 50g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr. In an alternateembodiment, the conversion of olefin monomer is at least 10%, based uponpolymer yield and the weight of the monomer entering the reaction zone,preferably 20% or more, preferably 30% or more, preferably 50% or more,preferably 80% or more.

In a preferred embodiment, little or no alumoxane is used in the processto produce the polymers. Preferably, alumoxane is present at zero mol %,alternately the alumoxane is present at a molar ratio of aluminum totransition metal less than 500:1, preferably less than 300:1, preferablyless than 100:1, preferably less than 1:1.

In a preferred embodiment, little or no scavenger is used in the processto produce the ethylene polymer. Preferably, scavenger (such as trialkyl aluminum) is present at zero mol %, alternately the scavenger ispresent at a molar ratio of scavenger metal to transition metal of lessthan 100:1, preferably less than 50:1, preferably less than 15:1,preferably less than 10:1.

In a preferred embodiment, the catalyst system used in thepolymerization comprises no more than one metallocene compound. A“reaction zone” also referred to as a “polymerization zone” is a vesselwhere polymerization takes place, for example a batch reactor. Whenmultiple reactors are used in either series or parallel configuration,each reactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In a preferred embodiment, the polymerizationoccurs in one reaction zone. Room temperature is 23° C. unless otherwisenoted.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

A solution polymerization as used herein means a polymerization processin which the polymer is dissolved in a liquid polymerization medium,such as an inert solvent or monomer(s) or their blends. A solutionpolymerization is typically homogeneous. A homogeneous polymerization isone where the polymer product is dissolved in the polymerization medium.Such systems are preferably not turbid as described in J. VladimirOliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 29, 2000,4627.

A bulk polymerization as used herein means a polymerization process inwhich the monomers and/or comonomers being polymerized are used as asolvent or diluent using little or no inert solvent as a solvent ordiluent. A small fraction of inert solvent might be used as a carrierfor catalyst and scavenger. A bulk polymerization system contains lessthan 25 wt % of inert solvent or diluent, preferably less than 10 wt %,preferably less than 1 wt %, preferably 0 wt %.

Polyolefin Products with Internal Unsaturation Structures

This invention also relates to compositions of matter produced by themethods described herein.

In a preferred embodiment, the process described herein producesethylene homopolymers or ethylene copolymers, such asethylene-alphaolefin (preferably C₃ to C₂₀ alpha olefin) copolymers(preferably, such as ethylene-propylene, ethylene-butene,ethlene-hexene, or ethylene-octene copolymers) preferably having: aMw/Mn of greater than 1 to 4 (preferably greater than 1 to 3).

Likewise, the processes of this invention produce homopolymers orcopolymers of ethylene, where the ethylene copolymers preferably havefrom 0 to 25 mol % (alternately from 0.5 to 20 mol %, alternately from 1to 15 mol %, preferably from 3 to 10 mol %) of one or more C₃ to C₂₀olefin comonomer (preferably C₃ to C₁₂ alpha-olefin, preferablypropylene, butene, hexene, octene, decene, dodecene, preferablypropylene, butene, hexene, octene), or are copolymers of ethylenepreferably having from 0 to 25 mol % (alternately from 0.5 to 20 mol %,alternately from 1 to 15 mol %, preferably from 3 to 10 mol %) of one ormore of C₃ to C₂₀ olefin comonomer (preferably C₃ to C₁₂ alpha-olefin,preferably propylene, butene, hexene, octene, decene, dodecene,preferably ethylene, butene, hexene, or octene).

In a preferred embodiment, the monomer is ethylene and the comonomer ishexene, preferably from 1 to 15 mol % hexene, alternately 1 to 10 mol %.

Typically, the polymers produced herein have an Mw of 5,000 to 1,000,000g/mol (preferably 25,000 to 750,000 g/mol, preferably 100,000 to 500,000g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternately 1.2 to 20,alternately 1.3 to 10, alternately 1.4 to 5, 1.5 to 4, alternately 1.5to 3).

Typically, the polymers produced herein have a melt index (MI, alsoreferred to as 12, determined according to ASTM D1238, 190° C., 2.16 kgload) of 20 dg/min or less, preferably 10 dg/min or less, preferably 5dg/min or less, preferably 1.0 dg/min or less, preferably 0.9 dg/min orless, preferably 0.8 dg/min or less, preferably 0.7 dg/min or less,alternately from 0.01 to 20 dg/min, preferably from 0.01 to 10 dg/min,preferably from 0.05 to 5 dg/min, preferably from 0.1 to 1.0 dg/min,preferably from 0.2 to 0.9 dg/min.

In a preferred embodiment, the polymer produced herein has a unimodal ormultimodal molecular weight distribution as determined by Gel PermeationChromotography (GPC). By “unimodal” is meant that the GPC trace has onepeak or inflection point. By “multimodal” is meant that the GPC tracehas at least two peaks or inflection points. An inflection point is thatpoint where the second derivative of the curve changes in sign (e.g.,from negative to positive or vice versa).

Unless otherwise indicated Mw, Mn, and MWD are determined by GPC asdescribed in US 2006/0173123, pp. 24-25, paragraphs [0334] to [0341].

In a preferred embodiment, the polymer produced herein has a compositiondistribution breadth index (CDBI) of 50% or more, preferably 60% ormore, preferably 70% or more. CDBI is a measure of the compositiondistribution of monomer within the polymer chains and is measured by theprocedure described in PCT publication WO 93/03093, published Feb. 18,1993, specifically columns 7 and 8, as well as in Wild et al, J. Poly.Sci., Poly. Phys. Ed., Vol. 20, p. 441, (1982) and U.S. Pat. No.5,008,204, including that fractions having a weight average molecularweight (Mw) below 15,000 are ignored when determining CDBI.

In a preferred embodiment the polymer produced herein has an internalunsaturation of 50% or more, preferably 60% or more, preferably 70% ormore.

The polyolefins are unique with respect to higher levels of internalunsaturation structures, which even exceeds the amount of end groupstheoretically possible for a polymer. Without wishing to bound by anyparticular theory, a possible intenal unsaturation structures formationmechanism is disclosed at Macromolecules 2005, 38, 6988, where internalvinylenes have been attributed to occur through the following mechanism.

For purposes of this invention and the claims thereto, unsaturations ina polymer are determined by ¹H NMR with reference to Macromolecules2014, 47, 3782 and Macromolecules 2005, 38, 6988, but in event ofconflict Macromolecules 2014, 47, 3782 shall control. Peak assignmentsare determined referencing the solvent of tetrachloroethane-1,2 d₂ at5.98 ppm. Specifically, percent internal unsaturation is determined byadding Vy1+Vy2+trisubstituted olefins then dividing by totalunsaturation. For example, for polymer 7.1 in Table 2, the percentinternal unsaturation is [(0.22+0.02)/0.31]×100=77.4. Thus, the polymerproduced in Example 7.1 has an internal unsaturation of 77.4%.

Advantageously, the polymers produced herein have an internalunsaturation of 50% or more, preferably 60% or more, preferably 70% ormore, alternately from 50 to 90%, from 60 to 85%, from 60 to 80%.

Blends

In another embodiment, the polymer (preferably the polyethylene orpolypropylene) produced herein, is combined with one or more additionalpolymers prior to being formed into a film, molded part, or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In a preferred embodiment, the polymer (preferably the polyethylene orpolypropylene) is present in the above blends, at from 10 to 99 wt %,based upon the weight of the polymers in the blend, preferably 20 to 95wt %, even more preferably at least 30 to 90 wt %, even more preferablyat least 40 to 90 wt %, even more preferably at least 50 to 90 wt %,even more preferably at least 60 to 90 wt %, and even more preferably atleast 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS' 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

Specifically, any of the foregoing polymers, such as the foregoingpolypropylenes or blends thereof, may be used in a variety of end-useapplications. Such applications include, for example, mono- ormulti-layer blown, extruded, and/or shrink films. These films may beformed by any number of well known extrusion or coextrusion techniques,such as a blown bubble film processing technique, wherein thecomposition can be extruded in a molten state through an annular die andthen expanded to form a uni-axial or biaxial orientation melt prior tobeing cooled to form a tubular, blown film, which can then be axiallyslit and unfolded to form a flat film. Films may be subsequentlyunoriented, uniaxially oriented, or biaxially oriented to the same ordifferent extents. One or more of the layers of the film may be orientedin the transverse and/or longitudinal directions to the same ordifferent extents. The uniaxially orientation can be accomplished usingtypical cold drawing or hot drawing methods. Biaxial orientation can beaccomplished using tenter frame equipment or double bubble processes andmay occur before or after the individual layers are brought together.For example, a polyethylene layer can be extrusion coated or laminatedonto an oriented polypropylene layer or the polyethylene andpolypropylene can be coextruded together into a film then oriented.Likewise, oriented polypropylene could be laminated to orientedpolyethylene or oriented polyethylene could be coated onto polypropylenethen optionally the combination could be oriented even further.Typically, the films are oriented in the Machine Direction (MD) at aratio of up to 15, preferably between 5 and 7, and in the TransverseDirection (TD) at a ratio of up to 15, preferably 7 to 9. However, inanother embodiment, the film is oriented to the same extent in both theMD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In a preferred embodiment, one or both of thesurface layers is modified by corona treatment.

In another embodiment, this invention relates to:

1. A process to polymerize olefins comprising:1) contacting olefin monomers with a catalyst system comprising anactivator and a bis-cyclopentadienyl metallocene compound represented bythe formula:

wherein:

M is Hf;

each X¹ and X² is independently, a hydrocarbyl radical having from 1 to20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide,diene, amine, phosphine, ether, or X¹ and X² may form a part of a fusedring or a ring system;each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen,halide, alkoxide or a C₁ to C₄₀ (preferably C₁ to C₂₀) substituted orunsubstituted hydrocarbyl group, provided that at least one (preferablyat least two) of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is a linear C₃ toC₂₀ substituted or unsubstituted hydrocarbyl group, alternately providedthat at least one of R⁶, R⁷, R⁸, and R⁹ and at least one of R¹, R², R³,R⁴, is a linear C₃ to C₂₀ substituted or unsubstituted hydrocarbylgroup;T is a group 14 atom (preferably, silicon or germanium; more preferably,silicon);each R^(a) and R^(b) is independently, a C₁ to C₄₀ substituted orunsubstituted hydrocarbyl, (preferably a C₁ to C₂₀ substituted orunsubstituted alkyl, or a C₆ to C₂₀ substituted or unsubstituted aryl);wherein the bis-cyclopentadienyl metallocene compound generates hydrogenand the polymerization occurs in the presence of hydrogen, preferably atleast 200 ppm hydrogen;2) obtaining a polymer having:

a) an internal unsaturation of 50% or more;

b) a melt index of 20 dg/min or less, preferably a melt index of 1.0dg/min or less; and

c) a g′vis of 0.95 or more.

2. The process of paragraph 1, wherein each X¹ and X² is, independently,selected from the group consisting of halides and C₁ to C₅ alkyl groups.3. The process of paragraphs 1-2, wherein each X¹ and X² is,independently, selected from the group consisting of chlorides,fluorides, methyl, and ethyl groups.4. The process of paragraphs 1-3, wherein at least one of R⁶, R⁷, R⁸,and R⁹ and at least one of R¹, R², R³, R⁴, is a linear C₃ to C₁₀unsubstituted hydrocarbyl group.5. The process of paragraphs 1-3, wherein each R², R³, R⁴, R⁶, R⁷, R⁸,and R⁹ is, independently, a linear C₃ to C₂₀ alkyl group, preferably ann-propyl, n-butyl, n-pentyl, and n-hexyl group.6. The process of paragraphs 1-3, wherein at least one of R² and R³ andat least one of R⁷ and R⁸ is, independently, selected from the groupconsisting of n-propyl, n-butyl, n-pentyl, and n-hexyl groups.7. The process of paragraphs 1-6, wherein each R^(a) and R^(b) is,independently selected from the group consisting of C₁ to C₂₀ alkyls,phenyl, and substituted phenyl groups.8. The process of paragraphs 1-7, wherein the metallocene compoundcomprises one or more of:diphenylsilylbis(n-propylcyclopentadienyl)hafnium X¹X²,diphenylsilylbis(n-butylcyclopentadienyl)hafniumX¹X²,diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X², diphenylsilyl(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX¹X²,diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X²,dimethylsilylbis(n-propylcyclopentadienyl)hafniumX¹X²,dimethylsilylbis(n-butylcyclopentadienyl)hafniumX¹X²,dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X², dimethylsilyl(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX¹X²,dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X²,wherein each X¹ and X² is, independently, selected from the groupconsisting of chlorides, fluorides, methyl, ethyl, propyl, and butylgroups.9. The process of paragraphs 1-8, wherein the activator comprisesalumoxane.10. The process of paragraph 9, wherein the alumoxane is present at amolar ratio of aluminum to transition metal of the metallocene compoundof 100:1 or more.11. The process of paragraphs 1-10, wherein the activator comprises anon-coordinating anion activator.12. The process of paragraphs 1-11, wherein the activator is representedby the formula:

(Z)_(d) ⁺(A^(d−))

wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base;H is hydrogen; (L-H)⁺is a Bronsted acid; A^(d−) is a non-coordinatinganion having the charge d−; and d is an integer from 1 to 3.13. The process of claim paragraphs 1-12, wherein the activator is oneor more of: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph3C+][B(C₆F5)4−],[Me3NH+][B(C₆F5)4−],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate), trialkylammoniumtetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate,wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.14. The process of claim paragraphs 1-13, wherein the olefin monomercomprises ethylene.15. The process of paragraphs 1-14, wherein the catalyst system issupported on an inert support material.16. The process of paragraphs 1-15, wherein the catalyst system issupported on a support material selected from the group consisting oftalc, inorganic oxides, zeolites, clays, organoclays and mixturesthereof17. The process of claim paragraphs 1-16, wherein step 1) occurs at atemperature of from about 0° C. to about 300° C., at a pressure in therange of from about 0.35 MPa to about 10 MPa, and at a time of up to 300minutes.18. A catalyst system comprising an activator and a bis-cyclopentadienylmetallocene compound represented by the formula:

wherein:

M is Hf;

each X¹ and X² is independently, a hydrocarbyl radical having from 1 to20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide,diene, amine, phosphine, ether, or X¹ and X² may form a part of a fusedring or a ring system;each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen,halide, alkoxide or a C₁ to C₄₀ (preferably C₁ to C₂₀) substituted orunsubstituted hydrocarbyl group, provided that at least one, preferablyat least two, of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹, is a linear C₃ toC₂₀ substituted or unsubstituted hydrocarbyl group;T is a group 14 atom (preferably, silicon or germanium; more preferably,silicon); each R^(a) and R^(b) is independently, a C₁ to C₄₀ substitutedor unsubstituted hydrocarbyl, (preferably a C₁ to C₂₀ substituted orunsubstituted alkyl, a C₆ to C₂₀ substituted or unsubstituted aryl).19. The catalyst system of paragraph 18, wherein each X¹ and X² is,independently, selected from the group consisting of halides and C₁ toC₅ alkyl groups.20. The catalyst system of paragraphs 18-19, wherein each X¹ and X² is,independently, selected from the group consisting of chlorides,fluorides, methyl, and ethyl groups.21. The catalyst system of paragraphs 18-20, wherein each R², R³, R⁴,R⁶, R⁷, R⁸, and R⁹ is, independently, a linear C₃ to C₂₀ alkyl group.22. The catalyst system of paragraphs 18-21, wherein at least one of R²and R³, R⁴ and at least one of R⁷ and R⁸ is, independently, selectedfrom the group consisting of n-propyl, n-butyl, n-pentyl, and n-hexylgroups.23. The catalyst system of paragraphs 18-22, wherein each R^(a) andR^(b) is, independently selected from the group consisting ofsubstituted or unsubstituted C1 to C₂₀ aklyls, phenyl, and substitutedphenyl groups.24. The catalyst system of paragraphs 18-23, wherein the metallocenecompound comprises one or more of:

-   diphenylsilylbis(n-propylcyclopentadienyl)hafnium X¹X²,-   diphenylsilylbis(n-butylcyclopentadienyl)hafniumX¹X²,-   diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X²,-   diphenylsilyl (n-propyl    cyclopentadienyl)(n-butylcyclopentadienyl)hafniumX¹X²,-   diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X²,-   dimethylsilylbis(n-propylcyclopentadienyl)hafniumX¹X²,-   dimethylsilylbis(n-butylcyclopentadienyl)hafniumX¹X²,-   dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X²,-   dimethylsilyl (n-propyl cyclopentadienyl)(n-butyl    cyclopentadienyl)hafniumX¹X²,-   dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X²,    wherein each X¹ and X² is, independently, selected from the group    consisting of chlorides, fluorides, methyl, ethyl, propyl, and butyl    groups.    25. An ethylene polymer having: a) an internal unsaturation of 50%    or more; b) a melt index of 20 dg/min or less, preferably 1.0 dg/min    or less; and c) a g′vis of 0.95 or more.    26. A film comprising the polymer of paragraph 25.    27. A tie layer in a film comprising the polymer of paragraph 25.

Test Methods

¹H NMR

¹H NMR data was collected at 120° C. using a 10 mm CryoProbe with aBruker spectrometer at a ¹H frequency of 600 MHz (available from BrukerCorporation, United Kingdom). Data were recorded using a maximum pulsewidth of 45°, 5 seconds between pulses and signal averaging 512transients. Samples were prepared by dissolving 80 mg of sample in 3 mLof solvent heated at 140° C. For purposes of this invention and theclaims thereto, unsaturations in a polymer are determined by ¹H NMR withreference to Macromolecules, 2014, 47, 3782 and Macromolecules, 2005,38, 6988, but in event of conflict Macromolecules, 2014, 47, 3782, shallcontrol. Peak assignments are determined referencing the solvent oftetrachloroethane-1,2 d₂ at 5.98 ppm.

GPC-DRI

Mn (GPC), Mw, Mz and g′(vis) were determined using a Gel PermeationChromatography (GPC) method using a High Temperature Size ExclusionChromatograph (SEC, either from Waters Corporation, Milford, Mass. orPolymer Laboratories (now part of Varian Inc., available from AgilentTechnologies)), equipped with a differential refractive index detector(DRI). Experimental details are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001), and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate was 0.5cm³/min and the nominal injection volume is 300 μL. The various transferlines, columns, and differential refractometer (the DRI detector) werecontained in an oven maintained at 135° C. Solvent for the SECexperiment was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB was then degassed with an online degasser before entering the SEC.Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units were 1.463 g/mL at room temperatureand 1.324 g/mL at 135° C. The injection concentration was from 1.0 to2.0 mg/mL, with lower concentrations being used for higher molecularweight samples. Prior to running each sample, the DRI detector and theinjector were purged. Flow rate in the apparatus was then increased to0.5 mL/minute and the DRI was allowed to stabilize for 8 to 9 hoursbefore injecting the first sample. The concentration, c, at each pointin the chromatogram was calculated from the baseline-subtracted DRIsignal, using the following equation:

c=K _(DRI) T _(DR)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto, (dn/dc)=0.104 for propylene polymersand ethylene polymers and 0.1 otherwise. Units of parameters usedthroughout this description of the SEC method were: concentration wasexpressed in g/cm³, molecular weight was expressed in g/mol, andintrinsic viscosity was expressed in dL/g.

The resultant polymer is analyzed by GPC to determine the molecularweight and by DRI to determine percent of 1-hexene incorporation.

Polymers produced by the processes of this invention also have a g′(vis)of greater than 0.95 (preferably greater than 0.96, preferably greaterthan 0.98, preferably greater than 0.99, and, optionally, preferablyless than or equal to 1.0). The branching index (g′(vis)) is calculatedusing the output of the SEC-DRI-LS-VIS method as follows. The averageintrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\Sigma \; {c_{i}\lbrack\eta\rbrack}_{i}}{\Sigma \; c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits, wherein [η]_(i) is the intrinsic viscosity over thechromatographic slices, i.

The branching index g′(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

All molecular weights are weight average unless otherwise noted. Allmolecular weights are reported in g/mol unless otherwise noted.

Melt index (MI) also referred to as 12, reported in g/10 min, isdetermined according to ASTM D1238, 190° C., 2.16 kg load.

High load melt index (HLMI) also referred to as 121, reported in g/10min, is determined according to ASTM D1238, 190° C., 21.6 kg load.

Melt index ratio (MIR) is MI divided by HLMI as determined by ASTMD1238.

Density is determined according to ASTM D1505.

Bulk density is measured by quickly transferring (in 10 seconds) thesample powder into a graduated cylinder which overflows when exactly 100cc is reached. No further powder is added at this point. The rate ofpowder addition prevents settling within the cylinder. The weight of thepowder is divided by 100 cc to give the density.

EXAMPLES

All reactions were carried out under inert atmosphere, preferablynitrogen, unless otherwise stated. All solvents were obtained from SigmaAldrich Co. and dried before use over 3A molecular sieves (also obtainedfrom Sigma Aldrich), unless otherwise stated.Bis(n-propyl-cyclopentadienyl)hafnium dimethyl was purchased fromBoulder. ¹H NMR measurements for catalyst syntheses were recorded on a400 Mz Bruker spectrometer.

The following abbreviations used herein: Catalyst 1 is dimethylsilylbis(3-n-propyl cyclopentadienyl) hafnium dimethyl; Catalyst 2 isdiphenylsilylbis (3-n-propyl cyclopentadienyl) hafnium dimethyl;Catalyst 3 is (1,3-MeBuCp)₂ZrCl₂; MAO is methylalumoxane; and TIBAL istriisobutylaluminum. MAO is obtained from Albemarle (Baton Rouge, La.)and TIBAL is obtained from Sigma Aldrich Co. (St. Louis, Mo.), and bothwere used as received, unless otherwise stated.

Example 1: Synthesis of rac/meso Me₂Si(3-n-PropylCp)₂HfMe₂ (Catalyst 1

A solution of dimethylsilyl dichloride (3.0 g) in THF was cooled in afreezer to −25° C. To this was added 5.3 g of n-propylcyclopentadieneand stirred for 12 h. The solvent was removed in vacuo to give an offwhite solid. Pentane was added and the slurry stirred for 1 h. Theslurry was then filtered through a glass frit and evaporated to give 6.3g of a yellow oil.

The resulting dimethylsilylbis(n-propylcyclopentadiene) was dissolved inTHF and cooled to −25° C. Next, 18.4 mL of a 2.5M solution ofn-butyllithium in hexane was added slowly to the solution. The reactionwas allow to stir 12 h after which the solvent was removed in vacuo. Thereaction was slurried in pentane and the solvent was filtered off togive an off-white powder (4.7 g), which was dried in vacuo.

The 4.7 g of lithium diphenylsilylbis(n-propylcyclopentadienide) wasadded to a slurry of 5.2 g of HfCl₄ in diethyl ether that had beencooled to −25° C. After stirring for 12 h the reaction was filteredthrough a glass frit and dried in vacuo to give a light orange oil. Thiswas dissolved in pentane, filtered and the filtrate dried in vacuo togive a light orange oil (4.1 g).

The resulting dimethylsilylbis(n-propylcyclopentadienyl) hafniumdichloride was dissolved in THF and cooled to −25° C. Methyl magnesiumbromide (6.6 mL) was then added slowly and left to stir for 12 h. Thesolvent was then removed in vacuo to a dark orange oil that was thendissolved in pentane. The reaction was filtered and the solvent removedin vacuo to give 3.95 g of a dark orange viscous oil of rac/mesodimethylsilylbis(3-n-propylcyclopentadienyl) hafnium dimethyl. ¹H NMR(400 MHz, CDCl₂) δ 6.45 (1H, t), 6.42 (1H, t), 5.59 (1H, t), 5.48 (1H,t), 5.37 (1H, t), 5.29 (1H, t), 2.64-2.49 (4H, m), 1.66-1.60 (4H, m),0.98 (6H, t), 0.46 (6H, t), −0.74 (6H, t).

Example 2: Synthesis of rac/meso Ph₂Si(3-n-PropylCp)₂HfMe₂ (Catalyst 2

A solution of diphenylsilyl dichloride (5.0 g) in THF was cooled to −25°C. To this solution 4.5 g of n-propyl cylopentadiene was added andstirred for 12 h. The solvent was then removed in vacuo to give a lightorange oil. This oil was dissolved in pentane, filtered through a glassfrit, evaporated in vacuo to give 7.1 g of orange oil.

Next, 5.0 g of the resulting diphenylsilyl(bis-n-propylcyclopentadiene)was dissolved in THF and cooled to −25° C. Then 10.0 mL of a 2.5Msolution of n-butyllithium in hexane was added slowly to the stirringsolution. This was allowed to stir for 6 h before removing the solventin vacuo. Next, the reaction was slurried in pentane and the solventfiltered off. The resulting white powder (1.94 g) was dried in vacuo.

The 1.94 g of diphenylsilyl(bis-lithium n-propyl cyclopentadiene) wasadded to a slurry of 1.7 g of HfCl₄(OEt₂)₂ in diethyl ether that wascooled to −25° C. After stirring for 12 h the reaction was filtered andthen dried in vacuo. The resulting orange oil was dissolved in pentane,filtered through a glass frit and the filtrate dried in vacuo to aviscous yellow oil (1.8 g).

The resulting diphenylsilyl(bis-n-propylcyclopentadienyl) hafniumdichloride (1.8 g) was dissolved in diethyl ether and cooled to −25° C.Methyl magnesium bromide (1.9 mL) was then added slowly and left to stirfor 12 h. The solvent was then removed in vacuo to an orange oil thendissolved in pentane. The reaction was then filtered and the pentaneremoved in vacuo to give 1.7 g of an orange viscous oil of rac/mesodiphenylsilyl(bis-3-n-propylcyclopentadienyl) hafnium dimethyl. ¹H NMR(400 MHz, CDCl₂) δ 7.92 (4H, t), 7.48 (6H, t), 6.57 (2H, d), 5.75 (1H,s), 5.67 (1H, s), 5.54 (1H, s), 5.50 (1H, s), 2.68-2.54 (4H, m), 1.71(4H, m), 1.05 (6H, t), −0.67 (6H, t).

Example 3: Preparation of Support

3.1 Preparation of sMAO-a

Davison 948 silica (40.7 g), calcined at 600° C. for 2 hours, wasslurried in 200 mL of toluene. MAO (71.4 g of a 30% wt toluene solution,351.1 mmol of Al) was added slowly to the slurry. The slurry was thenheated to 80° C. and stirred for 1 hr. The slurry was filtered, washedthree times with 70 mL of toluene and once with pentane. The solid wasdried under vacuum overnight to give a 60.7 g amount of free flowingwhite solid.

3.2 Preparation of sMAO-b

Fluorided D948 silica preparation: 1.18 g (NH₄)₂SiF₆ was dissolved in7.00 g water in a 20 ml glass vial, 50 g raw Grace D948 silica and 200 gof toluene were combined in a 250 ml celstir. Under vigorous stirring,the aqueous solution of (NH₄)₂SiF₆ was added via a syringe to thetoluene slurry. The mixture was allowed to stir at room temperature for2.5 h. The milky slurry was filtered through a 500 ml Optichemdisposable polyethylene frit (40 micron), rinsed with 200 g pentane forthree times, then dried in air overnight to yield a white, free-flowingsolid. The solid was transferred into a tube furnace, and was heated to200° C. under constant nitrogen flow (temperature program: 25° C./hramped to 150° C.; held at 150° C. for 4 hours; 50° C./h ramped to 200°C.; held at 200° C. for 4 hours; cooled down to room temperature). 46 gof fluorided D948 was collected after the calcination. CalculatedF-loading: 0.8 mmol/g (F-loading=mmol of F/gram of added raw silica).

sMAO-b preparation: MAO (37.6 g of 30% wt in toluene) was added to a 250ml celstir along with 100 mL of toluene. 29.9 g fluorided D948 silicawas prepared in the previous step and was added to the slurry in 5 gincrements. The reaction was stirred for 10 minutes at room temperatureand was then heated to 100° C. for 3 hours. The solid was filtered,washed twice with 80 mL of toluene, washed twice with pentane, and driedunder vacuum overnight. 39.6 g of free flowing white solid wascollected.

Example 4: Preparation of Supported Catalysts 4.1 Supported Catalyst a

Rac/meso Ph₂Si(3-nPrCp)₂HfMe₂ (0.0284 g, 0.0471 mmol) was dissolved in 7milliliters of toluene and added to a Celstir™ flask. A 1.18 gram amountof sMAO-a was added as a solid all at once to the Celstir™ flask andwashed down with 7 milliliters of toluene. The slurry was stirred atroom temperature for 1 hour. The solid was filtered, washed three timeswith 15 milliliters of toluene, and washed twice with pentane. The solidwas dried under vacuum to give a 1.09 gram amount of off-white powder.

4.2 Supported Catalyst B

Rac/meso Me₂Si(3-nPrCp)₂HfMe₂ (0.018 g, 0.0378 mmol) was dissolved in 3milliliters of toluene and added to a Celstir™ flask. A 0.949 gramamount of sMAO-a was added as a slurry in 15 mls of toluene all at onceto the Celstir™ flask and washed down with 7 milliliters of toluene. Theslurry was stirred at room temperature for 1 hour. The solid wasfiltered, washed three times with 15 milliliters of toluene, and washedtwice with pentane. The solid was dried under vacuum to give a 0.885gram amount of off-white powder.

4.3 Supported Catalyst C

1,3-MeBuCp₂ZrCl₂ was supported on silica (about 4 μmol/g) according tothe general procedure described in U.S. Pat. No. 6,180,736.

4.4 Supported Catalyst D

20.0 mg Catalyst 1 (dimethylsilylbis (3-n-propyl cyclopentadienyl)hafnium dimethyl, 42 μmol) was dissolved in 2.07 g of toluene in a 20 mlglass vial. 0.51 g sMAO-a was slurried in 2.0 g of toluene in a 20 mlglass vial. 1.0 gram of the Catalyst 1/toluene solution was added to thesMAO-a/toluene slurry via a pipette. The glass vial was capped with aTeflon-lined cap and vortexed at room temperature for 90 min. Theresulting slurry was filtered through a 18 mL polyethylene frit (10micron), and rinsed with 3 g toluene for 3 times, followed by 2 g ofpentane for 3 times. The collected solid was dried under vacuum for 40min. 0.488 g of supported Catalyst 1 was collected. Calculated catalystloading: 39 μmol/g (catalyst loading=μmol of catalyst/gram of addedsMAO-a).

4.5 Supported Catalyst E

20.0 mg Catalyst 1 (42 μmol) was dissolved in 2.07 g of toluene in a 20ml glass vial. 0.4920 g sMAO-b was slurried in 2.0 g of toluene in a 20ml glass vial. 1.00 gram of the Catalyst 1/toluene solution was added tothe sMAO-b/toluene slurry via a pipette. The glass vial was capped witha Teflon-lined cap and vortexed at room temperature for 90 min. Theresulting slurry was filtered through a 18 mL polyethylene frit (10micron), and rinsed with 3 g toluene for 3 times, followed by 2 g ofpentane for 3 times. The collected solid was dried under vacuum for 40min. 0.4700 g of supported Catalyst 1 was collected. Calculated catalystloading: 41 μmol/g (catalyst loading=μmol of catalyst/gram of addedsMAO-b).

4.6 Supported Catalyst F

Catalyst 2 (diphenylsilylbis (3-n-propyl cyclopentadienyl) hafniumdimethyl, 23.8 mg, 39 μmol) was combined with 1.00 gram of sMAO-b and4.0 gram of toluene in a 20 ml glass vial in the dry box. The glass vialwas capped with a Teflon-lined cap and vortexed at room temperature for90 min. The resulting slurry was filtered through a 18 mL polyethylenefrit (10 micron), and rinsed with 3 g toluene for 3 times, followed by 2g of pentane for 3 times. The collected solid was dried under vacuum for40 min. Calculated catalyst loading: 39 μmol/g (catalyst loading=μmol ofcatalyst/gram of added sMAO-b).

4.7 Supported Catalyst G

(n-prCp)₂HfMe₂ was supported on sMao-a (40 μmol/g) according to thegeneral procedure described in U.S. Pat. No. 6,180,736.

Momoners

Polymerization grade ethylene was used and further purified by passingit through a series of columns: 2250 ml Oxyclear cylinder from Labclear(Oakland, Calif.), followed by a 2250 cc column packed with dried 3 Åmole sieves purchased from Aldrich Chemical Company (St. Louis, Mich.),two 500 cc columns packed with dried 5 Å mole sieves purchased fromAldrich Chemical Company, one 500 cc column packed with ALCOA SelexsorbCD (7×14 mesh) purchased from Coastal Chemical Company (Abbeville, La.),and one 500 cc column packed with ALCOA Selexsorb COS (7×14 mesh)purchased from Coastal Chemical Company.

Polymerization grade 1-hexanes were further purified by passing itthrough a series of columns: two 500 cc Oxyclear cylinders from Labclearfollowed by two 500 cc columns packed with dried 3 Å mole sievespurchased from Aldrich Chemical Company and two 500 cc columns packedwith dried 5 Å mole sieves purchased from Aldrich Chemical Company andused.

1-Hexene was obtained from Sigma Aldrich (St. Louis, Mo.) and was driedover NaK amalgam.

Example 5: Slurry Phase Polymerization of Ethylene and 1-Hexene

Into a 1 L stainless steel autoclave reactor was added scavenger (TIBAL,as a 1-hexane solution) followed by 500 mls of isobutane. Ethylene wasadded (180 psi) and the reactor was heated to 80° C. with the stirringrate set at 750 rpm. The supported catalyst system was then added by ashort nitrogen purge through a small stainless steel bomb attachedsecurely to the reactor. Ethylene was maintained at the initial pressurethroughout the polymerization. The polymerization was allowed to proceedfor a set time at which time the reactor was cooled and excess pressurevented into the hood. The solid resin was transferred into anappropriate glass vessel and dried at 80° C. in a vacuum oven for atleast 2 hours. Process conditions and characterization results for theresins are summarized in Table 1.

As shown in Table 1, Catalyst 2 can be used to produce a polymer havinga higher Mw, which is more than 100,000 g/mol. The lower MIR valuesobtained for the resins indicates little or no long chain branching(LCB). The lack of LCB was further supported by the GPC trace whichyielded a g′vis value of approximately 1.0.

TABLE 1 Slurry Phase Polymerization of Ethylene and 1-Hexene SupportedHexene MI Mw Mn Mw/ Hexene Activity Example Catalyst in feed dg/min MIRg/mol g/mol Mn wt % gP/gsup. Cat. g′ (vis) 5.1 A 10 ml 0.566 18 150,00048,800 3.07 4.86 1328 1.004 5.2 B 10 ml 2.03 19 93,700 38,400 2.44 3.961668 1.016 5.3 C 10 ml 0.245 18.9 178,000 71,500 2.5 1.74 653

¹H NMR analysis of of the polymers indicates that there is significantinternal unsaturation structures as noted by triplet like peak (possiblytwo overlapping triplets) in the vinylene region of the ¹H NMR spectrumthat can be attributed to internal cis/trans olefins. References to beused for internal vinylenes assignments are the following:Macromolecules 2005, 38, 6988 and Macromolecules 2014, 47, 3782.

TABLE 2 Unsaturations per 1000 Carbons in E-H Copolymers E-H CopolymerEx 7.1 Ex 5.1 Ex. 5.2 Ex 5.3 7.3 Vy1 and Vy2 (cis and trans) 0.22 0.160.22 00.06 Vy5 0.05 0.07 0.07 00.04 Trisubstituted olefins 0.02 0.010.03 00.02 Vinyls (terminal) 0.00 0.02 0.02 0.06 Vinylidenes (terminal)0.02 0.01 0.01 0.02 Total unsaturation 0.31 0.27 0.35 0.2 % internalunsaturation 77.40% 62.90% 71.40% 40.0% (Vy1 + Vy2 + Trisub/totalunsaturation)

Example 6: High Throughput Polymerizations of Ethylene and 1-Hexene

Ethylene and 1-hexene copolymerizations were carried out in a parallelpressure reactor, as generally described in U.S. Pat. No. 6,306,658;U.S. Pat. No. 6,455,316; U.S. Pat. No. 6,489,168; WO 00/09255; andMurphy et al., J. Am. Chem. Soc., 2003, 125, pp. 4306-4317, each ofwhich is incorporated herein by reference for US purposes. Although thespecific quantities, temperatures, solvents, reactants, reactant ratios,pressures, and other variables are frequently changed from onepolymerization run to the next, the following describes a typicalpolymerization performed in a parallel pressure reactor. A pre-weighedglass vial insert and disposable stirring paddle were fitted to eachreaction vessel of the reactor.

The reactor was prepared as described above, and then purged withethylene. Isohexane, 1-hexene and TIBAL were added via syringe at roomtemperature and atmospheric pressure. The reactor was then brought toprocess temperature (85° C.) and charged with ethylene to processpressure (130 psig=896 kPa) while stirring at 800 RPM. A series ofsupported catalysts shown in Table 3, as prepared in Example 4 (100 μLof a 3 mg/mL toluene slurry, unless indicated otherwise), were added viasyringe with the reactor at process conditions. TIBAL was used as 200 μLof a 20 mmol/L in isohexane solution. Ethylene was allowed to enter(through the use of computer controlled solenoid valves) the autoclavesduring polymerization to maintain reactor gauge pressure (+/−2 psig).Reactor temperature was monitored and typically maintained within +/−1°C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar(5 mol % O₂) gas mixture to the autoclaves for approximately 30 seconds.The polymerizations were quenched after a predetermined cumulativeamount of ethylene had been added or for a maximum of 300 minutespolymerization time. The reactors were cooled and vented. The polymerwas isolated after the solvent was removed in-vacuo. Catalyst activityis calculated as kilograms of polymer per mol transition metal compoundper hour of reaction time (kg/mol·hr). Characterization results of theresins are summarized in Table 3.

TABLE 3 High Throughput Polymerization of Ethylene and 1-Hexene H₂ mol %PDI Supported level C6 Activity Mw (Mw/ wt % Catalyst (ppm) in feed(kg/mol · h) (kg/mol) Mn) C6 C 0 6 18193 461 2.0 2.4 300 6 21070 266 1.92.0 D 0 6 32359 314 2.2 3.8 E 0 6 33790 332 2.0 3.8 0 11 39081 433 2.05.4 300 6 35610 275 2.0 3.3 F 0 6 35011 394 2.1 4.2 0 11 40497 452 2.15.4 300 6 36697 278 1.9 4.4

As can be seen from Table 3, the present catalyst system shows animproved incorporation of hexene comonomer, and higher Mw more than100,000 g/mol. In addition, fluorided catalyst system (sMao-b) exhibitshigher activity and percent of comonmer incorporation.

Example 7: Gas Phase Polymerization of Ethylene and 1-Hexene

Polymerization was performed in a 7 foot tall gas-phase fluidized bedreactor with a 4 foot tall 6′ diameter body and a 3 foot tall 10′diameter expanded section. Cycle and feed gases were fed into thereactor body through a perforated distributor plate, and the reactor wascontrolled at 300 psi and 70 mol % ethylene. Reactor temperature wasmaintained by heating the cycle gas. Supported catalyst was fed as a 10wt % slurry in Sono Jell® from Sonneborn (Parsippany, N.J.). The slurrywas delivered to the reactor by nitrogen and isopentane feeds in a ⅛″diameter catalyst probe. Polymer was collected from the reactor asnecessary to maintain the desired bed weight. Average process conditionsare shown in Table 4.

TABLE 4 Example 7.1 7.2 7.3 Supported Catalyst B A G cat nameTemperature (° C.) 185 185 185 Pressure (psi) 300 299 295 Ethylene (mole%) 69.8 69.7 70.1 Hydrogen (ppm) 323 349 300 Hydrogen Flow (sccm) 4.985.24 13.14 H₂/C₂ Flow Ratio ((sccm H₂)/(g/hr C₂)) 0.003 0.003 0.007Hexene (mole %) 0.64 0.62 1.03 Bed Weight (g) 1596 2894 1574 ResidenceTime (hr) 3.8 7.5 2.9 Cycle Gas Velocity (ft/s) 1.58 1.54 1.58Production Rate (g/hr) 423 384 550 Activity (g_(poly)/g_(supported cat))1915 2207 2224 Catalyst Slurry Feed (cc/hr) 2.5 2 2.8 MI (g/10 min) 0.880.62 0.74 HLMI (g/10 min) 17.11 13.09 13.76 MIR 19.37 21.19 18.65Density (g/cm³) 0.9196 0.9227 0.9162 Bulk Density (g/cc) 0.3480 0.39970.3689 g′(vis) 1.024 N₂ Cat. Probe Feed (cc/min) 6000 6000 6000 iC₅ Cat.Probe Feed (g/min) 1 1 1

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise, whenever a composition,an element or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements and vice versa.

What is claimed is:
 1. A process to polymerize olefins comprising: contacting olefin monomers with a catalyst system comprising an activator and a bis-cyclopentadienyl metallocene compound represented by the formula:

wherein: M is Hf; each X¹ and X² is independently, a hydrocarbyl radical having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or X¹ and X² optionally form a part of a fused ring or a ring system; each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen, halide, alkoxide or a C₁ to C₄₀ substituted or unsubstituted hydrocarbyl group, provided that at least one of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is a linear C₃ to C₂₀ substituted or unsubstituted hydrocarbyl group; T is a group 14 atom; each R^(a) and R^(b) is independently, a C₁ to C₄₀ substituted or unsubstituted hydrocarbyl; and wherein the bis-cyclopentadienyl metallocene compound generates hydrogen and the polymerization occurs in the presence of hydrogen; 2) obtaining a polymer having: a) an internal unsaturation of 50% or more; b) a melt index of less than 20 g/10 min; and c) a g′vis of 0.95 or more.
 2. The process of claim 1, wherein each X¹ and X² is, independently, selected from the group consisting of halides and C₁ to C₅ alkyl groups.
 3. The process of claim 1, wherein each R^(a) and R^(b) is, independently a C₆ to C₂₀ substituted or unsubstituted aryl.
 4. The process of claim 1 or 3, wherein at least one of R⁶, R⁷, R⁸, and R⁹ and at least one of R¹, R², R³, R⁴, is a linear C₃ to C₂₀ substituted or unsubstituted hydrocarbyl group.
 5. The process of claim 1, wherein each R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, a linear C₃ to C₂₀ alkyl group.
 6. The process of claim 1, wherein at least one of R⁷ and R⁸ and at least one of R² and R³, is independently selected from the group consisting of n-propyl, n-butyl, n-pentyl, and n-hexyl groups.
 7. The process of claim 1, wherein each R^(a) and R^(b) is, independently selected from the group consisting of phenyl, and substituted phenyl groups.
 8. The process of claim 1, wherein the metallocene compound comprises one or more of: diphenylsilylbis(n-propylcyclopentadienyl)hafnium X¹X², diphenylsilylbis(n-butylcyclopentadienyl)hafniumX¹X², diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X², diphenylsilyl (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX¹X², diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X², dimethylsilylbis(n-propylcyclopentadienyl)hafniumX¹X², dimethylsilylbis(n-butylcyclopentadienyl)hafniumX¹X², dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X², dimethylsilyl (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX¹X², dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X², wherein each X¹ and X² is, independently, selected from the group consisting of chlorides, fluorides, methyl, ethyl, propyl, and butyl groups.
 9. The process of claim 1, wherein the activator comprises alumoxane.
 10. The process of claim 9, wherein the alumoxane is present at a molar ratio of aluminum to transition metal of the metallocene compound of 100:1 or more.
 11. The process of claim 1, wherein the activator comprises a non-coordinating anion activator.
 12. The process of claim 1, wherein the activator is represented by the formula: (Z)_(d) ⁺(A^(d−)) wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinating anion having the charge d−; and d is an integer from 1 to
 3. 13. The process of claim 1, wherein the activator is one or more of: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph3C+][B(C₆F5)4−], [Me3NH+][B(C₆F5)4−], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.
 14. The process of claim 1, wherein the olefin monomer comprises ethylene.
 15. The process of claim 1, wherein the catalyst system is supported on an inert support material.
 16. The process of claim 1, wherein the catalyst system is supported on support material selected from the group consisting of talc, inorganic oxides, zeolites, clays, organoclays and mixtures thereof.
 17. The process of claim 1, wherein step 1) occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time of up to 300 minutes.
 18. A catalyst system comprising hydrogen, an activator and a bis-cyclopentadienyl metallocene compound represented by the formula:

wherein: M is Hf; each X¹ and X² is independently, a hydrocarbyl radical having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or X¹ and X² optionally form a part of a fused ring or a ring system; each of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, hydrogen, halide, alkoxide or a C₁ to C₄₀ substituted or unsubstituted hydrocarbyl group, provided that at least one of R¹, R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is a linear C₃ to C₂₀ substituted or unsubstituted hydrocarbyl group; T is a group 14 atom; and each R^(a) and R^(b) is independently, a C₁ to C₄₀ substituted or unsubstituted hydrocarbyl.
 19. The catalyst system of claim 18, wherein each X¹ and X² is, independently, selected from the group consisting of halides and C₁ to C₅ alkyl groups.
 20. The catalyst system of claim 18, wherein each R^(a) and R^(b) is independently, a C₆ to C₂₀ substituted or unsubstituted aryl.
 21. The catalyst system of claim 18 or 20, wherein each R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, a linear C₃ to C₂₀ alkyl group.
 22. The catalyst system of claim 18, wherein each R², R³, R⁴, R⁶, R⁷, R⁸, and R⁹ is, independently, selected from the group consisting of n-propyl, n-butyl, n-pentyl, and n-hexyl groups.
 23. The catalyst system of claim 18, wherein at least one of R⁷ and R⁸ and at least one of R² and R³, is independently selected from the group consisting of n-propyl, n-butyl, n-pentyl, and n-hexyl groups and each R^(a) and R^(b) is, independently selected from the group consisting of C₁ to C₂₀ alkyl groups, phenyl, and substituted phenyl groups.
 24. The catalyst system of claim 18, wherein the metallocene compound comprises one or more of: diphenylsilylbis(n-propylcyclopentadienyl)hafnium X¹X², diphenylsilylbis(n-butylcyclopentadienyl)hafniumX¹X², diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X², diphenylsilyl (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX¹X², diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X², diphenylsilylbis(2-n-propylindenyl)hafniumX¹X², diphenylsilylbis(2-n-butylindenyl)hafniumX¹X², dimethylsilylbis(n-propylcyclopentadienyl)hafniumX¹X², dimethylsilylbis(n-butylcyclopentadienyl)hafniumX¹X², dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX¹X², dimethylsilyl (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX¹X², dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX¹X², wherein each X¹ and X² is, independently, selected from the group consisting of chlorides, fluorides, methyl, ethyl, propyl, and butyl groups.
 25. An ethylene polymer having: a) an internal unsaturation of 50% or more; b) a melt index of 1.0 dg/min or less; and c) a g′vis of 0.95 or more.
 26. A tie layer in a film, said tie layer comprising the polymer of claim
 25. 